EP2137271A1 - Mélange cristallin liquide polymérisable approprié pour le jet d'encre - Google Patents

Mélange cristallin liquide polymérisable approprié pour le jet d'encre

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Publication number
EP2137271A1
EP2137271A1 EP08716380A EP08716380A EP2137271A1 EP 2137271 A1 EP2137271 A1 EP 2137271A1 EP 08716380 A EP08716380 A EP 08716380A EP 08716380 A EP08716380 A EP 08716380A EP 2137271 A1 EP2137271 A1 EP 2137271A1
Authority
EP
European Patent Office
Prior art keywords
mixture according
polymerizable mixture
dyes
pigments
lcp
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP08716380A
Other languages
German (de)
English (en)
Inventor
Cees Bastiaansen
Thijs Meijer
Robert Jan Vrancken
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eindhoven Technical University
Original Assignee
Eindhoven Technical University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Eindhoven Technical University filed Critical Eindhoven Technical University
Priority to EP08716380A priority Critical patent/EP2137271A1/fr
Publication of EP2137271A1 publication Critical patent/EP2137271A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/34—Hot-melt inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
    • C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
    • C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
    • C09K2323/02—Alignment layer characterised by chemical composition
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]

Definitions

  • the present invention pertains to mixtures containing polymerizable liquid crystals and to a process for manufacturing the same in particular as authentication features for prevention of counterfeiting of documents and/or products.
  • LCP's Polymerizable Liquid Crystals
  • LCP's are a class of materials, which exhibit one or more liquid crystalline phases, such as a nematic, smectic or chiral nematic (also called cholesteric) phase, within a certain temperature range.
  • LCP's can be polymerized due to reactive groups, which are part of the molecule.
  • LCP's are monomers, but also after polymerization the resulting polymers are commonly referred to as LCP's.
  • LCP polymer In the text, where LCP's are mentioned the monomer form is referred to; the polymer form is referred to as LCP polymer.
  • LCP's Polymerization of LCP's can be induced spontaneously at elevated temperatures or aided by means of suitable initiators, such as for instance photo-initiators or thermal initiators.
  • suitable initiators such as for instance photo-initiators or thermal initiators.
  • reactive groups are acrylates, methacrylates, epoxies, oxethanes, vinyl-ethers, styrenes and thiol-enes.
  • monomers which by means of reactive end groups have the ability to form links with two other molecules are called mono-functional, since two links are the minimum number required to form a polymer.
  • Monomers with the ability to form links with more than two other molecules are called higher functional.
  • LCP-based authentication features Another method to create LCP-based authentication features is by inkjet printing of LCP's to form features with distinct optical properties. Furthermore, inkjet printing allows that each print is made unique, which is especially useful for instance when a need exists to track and trace each individual document or product or to include specific information such as biometric information. The possibility of combining LCP-based optical effects and inkjet printing is only mentioned in very few documents, which are all non-specific with regards to the actual requirements.
  • Printing LCP's with solvents has been described e.g. in EP1381520. Solvents are materials, which cause the LCP's to dissolve in them and together form a solution. Furthermore, such solvents are usually meant to evaporate after processing but before polymerization, so the solvent is not contained in any significant amount in the final product.
  • Examples of commonly employed solvents for LCP's are xylene, toluene and acetone.
  • the problem with ink jetting of LCP's is that commercial inkjet printing equipment is unable to reproducibly print LCP's if these are dissolved in solvents.
  • Ink jetting solvent-based mixtures leads to a drying effect, which is detrimental to the homogeneity of the prints, the so-called coffee stain effect.
  • the use of solvents can affect the substrates on which the LCP's are printed and also it can dissolve any previously printed LCP structure on the substrate before polymerization.
  • the use of solvent based mixtures gives rise to significant mixing of the materials on the substrate, leading to effects such as 'colour bleeding' and thus highly blurred images.
  • Solvents can also chemically attack parts of the print head or heads and conduits in the printing system, in particular polymer-based parts. These solvents also often evaporate at or near the nozzle, leading to clogging. Furthermore, such solvents are often harmful to the equipment because of corrugation as well as to people and to the environment due to toxicity and therefore require extensive equipment for air filtration near the printing equipment. Furthermore, heating of the printed materials to enhance evaporation and thus production speed is highly desirable, requiring heating installations within the production equipment which increase complexity and cost and also can be detrimental to the surrounding equipment as well as the substrates on which is being printed. For these reasons, a need exists to eliminate solvents from the process of inkjet printing of LCP's.
  • the mixture which is printed is at least chemically stable for the time it remains in the inkjet head or reservoir at the temperature at which the mixture is printed., which is in the order of minutes to weeks depending on the printing speed and printer usage,
  • the object of the present invention can be achieved with mixtures comprising the following components: a) 50-80wt% mono-functional LCP's, b) 10-50wt% of a higher functional LCP's, f) 0.01 -5wt% initiators, preferably below 1wt% g) 0.01 -5wt% inhibitors, preferably below 1wt% h) 0-20wt% additives, preferably below 10wt%, with the provision that the total amount of the components is 100wt% and wherein the polymerizable mixtures have a viscosity smaller than 0.015 Pa. s (which equals 15 mPa.s) at 100 0 C and yet remaining thermally stable.
  • EP1681586 discloses liquid crystalline layers as birefringent marking for decorative and security applications. This publication also mentions the possibility of using droplets of liquid crystal materials from melt, without going to any details regarding an inkjet process.
  • the polymerizable mixture in addition comprises c) 10-30wt% liquid crystalline inert monomers, preferably from 15-25wt%. Even more preferred the liquid crystalline inert monomer c) is a non-chiral monomer.
  • the polymerizable mixture additionally comprises d) 0.01- 30wt% non-liquid crystalline (mono- or higher) functionalized monomers.
  • the inventive polymerizable mixture in addition comprises e) 0.01-30wt% non-liquid crystalline inert monomers, preferably from 5 to 15wt%.
  • Components c), d) and e) can either be present together or separately in the mixture. It goes without saying, however, that the total amount of components forming the polymerizable mixture is always 100 wt.%.
  • the components a) (the mono- functional LCP's) and/or b) (the higher functional LCP's) are acrylates.
  • the polymerizable mixture is solvent-free.
  • the polymerizable mixture is particularly suitable for hot melt printing by inkjet printers.
  • the components from e) through f) are selected such that they do not prohibit the alignment of the liquid crystals from components a) through d).
  • the components from a), b) and d) are functionalized to form a polymer structure, more preferably due to possessing compatible types of functional groups, very preferable by possessing the same type of functional group.
  • the components a) through h) are selected such that phase-separation is suppressed at least only before polymerization but preferably also during polymerization that the mixture is homogeneous on the scale of individual ink jetted drops.
  • EP 1 422 283 discloses LC materials for printing without the need for high temperatures and without solvents. EP 1 422 283 does not disclose any temperature range. However the application discloses that the preferred viscosity of the LC mixture is 30 to 2000 centistokes, very preferably from 400-1000. Commercial standard inkjet printers need viscosities less than 15 mPa.s which equals 15 centistokes for a fluid of density 1 kg / liter.
  • ink jetting of solvent-free LCP's is easily possible.
  • the viscosity is not higher than 15 mPa.s at 100 0 C, and if the mixture is heated to decrease the viscosity, it remains thermally stable.
  • Ink Jet printing below 120° C, preferably below 100° C, very preferably 80° C is possible without problems, resulting in distinctive and reproducible optical effects.
  • a particular embodiment of the invention is the following mixture A, containing; a) 55.5wt% mono-functional LCP acrylate
  • Components a, b, c, f and g are subsequently added in a glass vial and the mixture is magnetically stirred for 15 minutes at 70 0 C.
  • the resulting mixture is clear and fluid at 70 0 C.
  • the viscosity of this mixture was measured using a rheometer using a parallel plate geometry and subsequently heated in an nitrogen flushed oven at 100 0 C for three weeks, after which the viscosity was measured again.
  • Table 1 viscosity of mixture A before and after heating at 100 0 C in a nitrogen environment for 3 weeks
  • Another preferred embodiment is the following mixture B: a) 53.5wt% mono-functional LCP acrylate
  • Components a, b, c, e, f and g are subsequently added in a glass vial and the mixture is magnetically stirred for 15 minutes at 70 0 C.
  • the resulting mixture is clear and fluid at 70 0 C.
  • the mixture was furthermore determined to still be photo-polymerizable and also still liquid crystalline and not phase-separated.
  • Another preferred embodiment is the following mixture C: a) 50.8wt% mono-functional LCP acrylate b) 20.8 wt% di-functional LCP acrylate c) 17.8% non-reactive LC monomer d) 9.9wt % non liquid crystalline functionalized monomers f) 0.6wt% photo-initiator
  • Components a, b, c, d, f and g are subsequently added in a glass vial and the mixture is magnetically stirred for 15 minutes at 70 0 C.
  • the resulting mixture is clear and fluid at 70 0 C.
  • the mixture was furthermore determined to still be photo- polymerizable and also still liquid crystalline and not phase-separated.
  • Mixture A was also tested in a heated Spectra inkjet printhead. Results showed stable printing was possible in range of 85°C - 120 0 C. Tests showed that the printing with Mixture A was stable for at least half an hour of continuous printing.
  • Acrylates have specific advantages in that they have fast curing times as well as a wide choice in suitable initiators.
  • LCP's with different reactive groups are also known from literature, and could also be applied with the same method.
  • Epoxies for instance have the specific advantages that they provide for good adhesion to many printed surfaces, exhibit relatively small amounts of polymerization shrinkage and are less affected by oxygen inhibition during polymerization.
  • Oxethanes have properties comparable to epoxies, but typically exhibit less polymerization shrinkage.
  • Thiol-ene based polymerization (including both thiol and -ene groups in the molecule structure) is also possible.
  • Vinyl-ethers are also not very sensitive to oxygen inhibition and polymerize very rapidly, but only at relatively high temperatures.
  • a suitable example of category e) is ethylene glycol.
  • Suitable examples of category f) are for instance sold by Ciba-Geigy (Switzerland), under the trade names lrgacure and Darocure, and in general polymerization initiators are known in the art. Combinations of different initiators can be used which has a number of potential advantages, of which a number are now described.
  • initiators will give different mechanical properties of the mixture before and after polymerization.
  • Using mono-functional initiators can allow for a low viscosity of the mixture.
  • multifunctional initiators tend to be more viscous.
  • the exact choice of initiators also influences e.g. the flexibility and toughness of the polymerized structure.
  • the choice of photo-initiator is dependent on the presence of other absorptive additives in the mixture, which will be described below at category h). It is possible to use mixtures of initiators, which in these cases to allow for a good polymerization of both the top layer of the structure as well as throughout the structure.
  • An initiator that can overcome oxygen inhibition of the surface can be used to initiate polymerization at the surface, whereas another initiators can be used to through-cure the structure. It is also possible to choose initiators in such a way that only the top of the structure polymerizes, but the remaining part remains non-polymerized. The non- polymerized LCP is then still fluid, and can be manipulated by means of for instance electric or magnetic fields, i.e. it remains switchable.
  • the list of possible additives from category h) contains, but is not limited to, the following examples.
  • additives molecules that can act as tracer molecules, such as e.g. DNA-molecules. These can be added in minute quantities, typically with amounts in the order of one part per million (ppm), so that they are very difficult to trace when their exact properties are not known beforehand.
  • Another example of additives is surfactants, which can enhance alignment of the liquid. These surfactants can either enhance the alignment of the liquid crystalline matrix at the top of the structure, at the bottom or in the bulk or in combinations of those locations. Furthermore, these surfactants can influence the potential phase separation of the mixture or influence the mechanical properties (e.g. viscosity, surface tension) of the mixture on the substrate or can perform a combination of these three functions.
  • chiral additives commonly referred to as chiral dopants, which are used to induce a chiral phase in liquid crystal structures.
  • Such chiral structures reflect light from a specific tunable wavelength range and with a specific handedness, which can either be commonly called left- or right-handed, and the handedness is determined by the handedness of the chirality of the structure.
  • one or more of the LCP's from categories a) through c) can also exhibit intrinsic chiral phases, and / or induce such a phase for all the liquid crystal molecules.
  • chiral LCP's By making use of chiral LCP's, a chiral structure can be obtained without the use of chiral additives.
  • the chiral additives are also polymerizable, which has the advantage that the temperature dependence of the reflected wavelength is usually decreased.
  • additives are pigments and dyes.
  • Pigments and dyes can be added to give the mixture an intrinsic color by means of absorption of part of the spectrum as well as optionally luminescence in part of the spectrum. Such intrinsic color can enhance the optical effects of the printed structure, for instance by enhancing contrast of (parts of) the printed structure.
  • Pigments are particles, which do not dissolve molecularly in the mixture whereas dyes can be approximately molecularly dissolved.
  • the choice between pigments and dyes is dependent on various factors.
  • One important factor is the solubility of the dyes or the pigments, with or without the aid of a dispersant, to create a stable ink. Solutions with dyes are generally easier to process than dispersions with pigments, but the optical properties of pigments are usually more stable.
  • certain optical additives are only available as pigments and not as dyes, such as di-electric stacks, whose optical effects are not based on molecular effects, but on effects on a larger scale.
  • Another important factor is the price of pigments, which is usually higher than that of dyes.
  • absorbing pigments or dyes are for instance
  • Non-reversible photochromic pigments and dyes which by excitation with light of a particular part of the spectrum reversibly change into another chemical species having a different absorption spectrum from the original chemical species.
  • Non-reversible photochromic pigments and dyes also exist for specific purposes
  • thermochromic pigments or dyes which exhibit a reversible change in absorption spectrum through the application of heat (i.e. at raised or lowered temperatures).
  • Non-reversible thermochromic pigments and dyes also exist for specific purposes
  • Electrochromic pigments or dyes which exhibit a change in absorption spectrum through the addition of electron charges
  • Halochromic pigments or dyes which exhibit a change in absorption spectrum through changes in pH.
  • Solvatochromic pigments or dyes which exhibit a change in absorption spectrum through changes in the polarity of the solvent which is in contact with them.
  • Tribochromic pigments or dyes which exhibit a change in absorption spectrum as a result of friction applied to them.
  • luminescent pigments or dyes examples are for instance
  • Fluorescent pigments or dyes which exhibit absorption of light in a particular part of the spectrum and emission in another part of the spectrum, typically at a lower wavelength, where the absorption and emission of individual photons occur subsequently but with delays of typically nano-seconds.
  • Phosphorescent pigments or dyes exhibit similar absorption and emission as fluorescent dyes, but due to a different quantum mechanical decay mechanism typically emit photons after absorption with much larger delays of up to hours or days.
  • Electroluminescent pigments or dyes which exhibit emission of photons as a result of radiative recombinations of electrons and holes within the pigments or dyes. Such radiative recombination can occur if an electric current is passed through the pigments or dyes, or alternatively of they are subjected to strong electric fields capable of exciting electron-hole pairs which subsequently recombine.
  • Triboluminescent pigments or dyes which exhibit emission of photons as a result of friction applied to them.
  • pigments or dyes which combine multiple optical effects within a single additive, or which is in fact an effect which is related to multiple causes concurrently. Examples are
  • Thermochromic pigment capsules which change colour if heated above a certain threshold temperature. At this temperature the crystalline solvent in the capsule melts and effectively lowers the pH. This in turn causes the halochromic compound present to change its absorptive properties.
  • Photochromic fluorescent dyes are dyes which exhibit fluorescence only after the molecule has absorbed photons from a part of the spectrum which it does not absorb in its subsequent fluorescent state. This effect which is concurrently photochromic and fluorescent, i.e. due to the first absorption not only the absorptive properties of the molecule changes (photochromism) but also the molecule subsequently exhibits fluorescence or a change in its fluorescent properties.
  • Pigments and dyes can exhibit anisotropic optical properties, depending on their molecular orientation, if anisotropic dye molecules aiign to a significant degree within the LCP matrix, typically parallel or perpendicular to the LCP alignment, typically caused by a distinct anisotropic molecular shape, these molecules can exhibit their anisotropic optical properties collectively, leading to distinctive optical effects, which remain after polymerization of the LCP matrix. This effect is commonly known as dichroism or pleochroism. Pigments can also exhibit dichroic effects if the particles as such have anisotropic optical properties. However, such properties are difficult to exploit since for a collective effect all pigments have to be effectively aligned in the direction of their inherent anisotropy.
  • UV-absorbing pigments and dyes or pigments can serve several specific purposes.
  • Such U V-protecting pigments and dyes can be present in the printed mixture or applied over the printed structure after curing by another printing step, preferably by means of flexography or offset printing.
  • other application methods can be employed, such as bar-coating, doctor blading, spraying or by applying a UV-absorbing substrate on top of the printed substrate.
  • these pigments or dyes absorb UV light, they can protect the printed layer, or the substance underneath this layer, from harmful UV-radiation which can lead to degradation of the (mechanical) properties of the structures, such as brittling.
  • UV-absorbers can also be used to prevent the deeper parts of the layer of being polymerized, thus allowing for a non- polymerized layer to exist, whereas the top layer is solidified during polymerization. Also, such a non-polymerized layer is not created but there is formed a gradient in the structure if specific components of the mixture diffuse towards or away from the higher polymerized regions during polymerization. Such gradients create new optical effects. For instance, a gradient in the amount of chiral dopant leads to structures after polymerization which exhibit a gradient in the chiral pitch, thus reflecting light over a greater wavelength range than a single pitched structure would. This effect is known as a broadband cholesteric mirror.
  • additives are conductive or semi-conductive additives.
  • Such additives can for example consist of the following group of additives:
  • oligothiophenes which are preferably LCP's.
  • Such conductive additives enable the printing of electronic circuits.
  • Such circuits can be used for instance to create optical effects which are switchable by means of electrical signals.
  • the conducting properties of the structure itself too can be used as an authentification feature. This can be done particularly effectively if elements of electronic circuits, such as FETs, diodes or capacitors are created within the print, since these give rise to designable and clearly identifiable electronic responses.
  • the conductive structures are used to make switchable another, adjacent non-conductive printed structure, either of which is not necessarily but preferably applied by means of inkjet printing.
  • Such multi- layered prints are advantageously created sequentially or concurrently, either in a single layer or in separate layers, printed either on top of or next to each other or even on opposite sides of the substrates or on multiple substrates which are assembled together after printing. Furthermore, it is possible to create structures which are conductive and contain electroluminescent or electrochromic additives, which can be addressed (made to change the optical appearance of the feature) by currents flowing through the printed structure itseif. Furthermore, by supplying charges of equal or opposite sign to two electrically isolated by adjacent parts of the structure, capacitators can be formed. If such parts of the structure are able to move mechanically, such movement can give rise to e.g. altered optical, mechanical, electrical or magnetic properties of the printed structure, which can be used to authenticate the feature.
  • the printed structures are (in part) made from LCP's, since the anisotropic properties of the aligned LCP polymer matrix can enhance the electrical and mechanical properties desired to fully exploit the conductive properties of the print.
  • additives are magnetic additives, such as paramagnetic, superparamagnetic, diamagnetic or ferri-magnetic particles. Such particles are typically 5 to 500nm in size. The addition of such particles enables the creation of structures that can be moved mechanically by means of magnetic fields. Again, such movement can give rise to e.g. altered optical, mechanical, electrical or magnetic properties of the printed structure, which can be used to authenticate the feature.
  • a particular benefit of adding (semi-) conductive or magnetic additives to the prints is that the authentication is straightforward by means of electric and magnetic fields or currents, and the effects can be reversible enabling non-destructive authentication. Furthermore, a particular benefit of inkjet printing such structures is that these additives can be printed in varying structures, thus enabling unique and identifiable responses to electrical or magnetic fields.
  • the printed structures are (in part) made from LCP's, since the anisotropic properties of the aligned LCP polymer matrix can enhance the electrical and mechanical properties desired to fully exploit the magnetic properties of the print.
  • the preferred substrates on which is printed induce or do not interfere with the alignment of the LCP's so as to obtain the desired optical effect.
  • Commonly used substrates are rubbed polyimide, as well as rubbed tri-acetyl-cellulose, polyethylene terephthalate, polyethylene or polypropylene. Rubbing causes planar aligning properties for these substrates.
  • LPP Linearly Photopolymerizable Polymers
  • SAM self-assembled mono-layers
  • the choice in substrates also determines the interactions between the mixture and the substrate. These interactions can be used to create additional (optical) effects.
  • additional (optical) effects E.g. the use of hydrophobic of hydrophilic (chemically) patterned surfaces allows for print confinement and thus a higher print resolution and more striking optical effects.
  • a geometrically patterned surface can also be used to confine printed ink. Confinement can lead to printed structures with more controlled geometries, leading to better defined properties which are beneficial for authentication purposes.
  • Such chemical or geometrical patterning of the substrates can be achieved by means of printing, but also other techniques such as for instance embossing, rubbing and lithography.
  • the optical properties of the employed substrates influence the overall properties of the security feature.
  • Such substrates can be combined, i.e. stacked on top of each other creating a multi-layered security feature, or a security feature created on a stack of substrates each having particularly beneficial properties.
  • the substrates can be transparent, absorbing in any range of wavelengths, scattering or reflecting or can comprise patterns of these effects.
  • the substrates can also have other optical properties. Examples are the ability to transmit only one polarization, as is the case with polarization films which transmit only one linear polarization, or the ability to reflect only one polarization, e.g. cholesteric films only reflect one handedness of light.
  • the substrates can change the polarization of transmitted or reflected light, as is the case with for instance retarder films and half wave plates.
  • the substrates can also contain other authentication features. Examples are holograms, retro-reflecting layers, interference stack reflectors, fluorescent layers, color-shifting layers or features printed by means of flakes. It is also possible to add layers containing other authentication features on top of the LCP polymer structures, via e.g. lamination.
  • the as-produced features are created such that they can be applied as tamper evident labels to products or documents.
  • Such labels have properties which render the intact removal of the labels very difficult. Such properties could be poor mechanical integrity, for instance features which have low toughness, i.e. low resistance to tearing.
  • the features upon removal can leave behind clear traces of its previous presence, for instance by means of rupture-sensitive ink particles.
  • the features can easily be applied to the documents and products. Such application can for instance be by means of hot-embossing or by creating self-adhesive features.
  • InkJet printing of LCP's is a very flexible technique, which allows for many novel optical designs, for instance by using multiple ink reservoirs which allows for the concurrent printing of inks with different optical properties.
  • the combination of normal black or colored inks with ink jet printing of LCP's can allow for the inclusion of features on top of normal printed information by printing retarding structures on top of an image or text printed with regular ink on a reflection substrate. It can also allow for the enhancement of contrast of cholesteric prints by printing cholesteric LCP mixtures on top of a strongly light absorbing image.
  • inks with identical apparent color but with different reflective properties such as left-hand and right-hand reflecting cholesteric LCP's
  • hidden information can be printed which can only be revealed using a polarization sensitive device or machine reader.
  • the combination of color-shifting non-liquid crystal ink layers and printed color-shifting LCP polymer layers creates a highly similar effect, as one ink has a uniform reflection and the other is polarization selective. Printing several layers on top of each other can enhance reflectivity or enhance the colors printed.
  • Self-authenticating structures can be printing by using e.g. structured polarizers and a birefringent LCP polymer layer on a reflective surface, which can be folded together to create additional effects. This can also recover encrypted data.
  • inkjet printing of LCP's it is possible to create authentication features with (multiple) overt, covert, forensic and biometric levels of security, which will be explained below.
  • additives such as pigments and dyes, substrates, printing procedures and designs of the layers present in the authentication features.
  • overt features which incorporate ieveis of security that are directly apparent (in particular visible) to anyone without the use of additional devices, like the color- shifting effect, which can be seen if a printed chiral nematic structure is tilted, are known as overt. Any overt security feature should be easily recognizable, but very difficult to counterfeit. Other examples are multi-color prints of chiral LCP polymer based color-shifting inks.
  • LCP's can be revealed using simple devices such as polarizers if choosing suitable designs.
  • polarizers nematic structures printed on a reflecting substrate, which shows reflection or no reflection when viewed through a polarizer at 0 or 45 degrees to the alignment axis.
  • Another example is a chiral LCP polymer print, which reflects only one handedness of circularly polarized light. This can be discerned by a circular polarizer.
  • Parts of the printed structure which could be left un-polymerized, could be electromagnetically switched if having anisotropic dielectric constants, as is the case for many inert liquid crystals. This changes the optical properties of the structures.
  • the covert level is not visible as a security feature (i.e. being without a combined overt level), but consists of e.g. (electro-) magnetically stored information, micro-text invisible to the eye, etc.
  • a security feature i.e. being without a combined overt level
  • covert level consists of e.g. (electro-) magnetically stored information, micro-text invisible to the eye, etc.
  • a more complicated level of security is the forensic level of security. This level is usually only known in detail by a selected group of users, who typically have access to expensive readout equipment. Possibilities for this level are to add tracer molecules to the mixture, which can be traced using highly advanced analysis techniques such as NMR scans. Other options are to analyze the exact ink content, or to investigate a specific size and shape of printed dots.
  • the biometric level of security allows a feature to store unique information, typically employed for e.g. tracking and tracing or authenticating persons. Due to the flexibility of the inkjet printing process of LCP's, it is possible to print e.g. barcodes, serial numbers, fingerprints and other information.
  • the combination of creating authentication features with clearly discemable optical features with the possibility to store unique information makes these features particularly interesting for secure tracking and tracing.
  • the visible security feature is discemable by consumers, the information is visual and therefore also easily detectable using very easy equipment such as barcode scanners or even camera's in mobile phones. These types of equipment can be easily connected to any type of database system, in which tracking and tracing information is stored.
  • the all visual features can also be used specifically in places where there are no other read-out devices are available due to equipment constraints.

Abstract

L'invention porte sur un mélange polymérisable approprié pour le jet d'encre, ayant des phases cristallines liquides comprenant les composants suivants : a) 50-80% en poids de phases cristallines liquides monofonctionnelles, b) 10-50% en poids de phases cristallines liquides de fonctionnalité supérieure, f) 0,01-5% en poids d'amorceurs, de préférence au-dessous de 1%, g) 0,01-5% en poids d'inhibiteurs, de préférence au-dessous de 1%, h) 0-20% en poids d'additifs, de préférence au-dessous de 10% en poids, à la condition que la quantité totale des composants soit de 100% en poids. Le mélange polymérisable est caractérisé par le fait qu'il a une viscosité inférieure à 0,015Pa.s à 100°C et qu'il reste néanmoins thermiquement stable.
EP08716380A 2007-03-13 2008-03-08 Mélange cristallin liquide polymérisable approprié pour le jet d'encre Withdrawn EP2137271A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08716380A EP2137271A1 (fr) 2007-03-13 2008-03-08 Mélange cristallin liquide polymérisable approprié pour le jet d'encre

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
EP07005120 2007-03-13
EP07005119 2007-03-13
EP07005122 2007-03-13
EP07005123 2007-03-13
PCT/EP2008/001868 WO2008110317A1 (fr) 2007-03-13 2008-03-08 Mélange cristallin liquide polymérisable approprié pour le jet d'encre
EP08716380A EP2137271A1 (fr) 2007-03-13 2008-03-08 Mélange cristallin liquide polymérisable approprié pour le jet d'encre

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EP2137271A1 true EP2137271A1 (fr) 2009-12-30

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EP08716431A Withdrawn EP2137272A1 (fr) 2007-03-13 2008-03-11 Dispositif de sécurité ayant des caractéristiques d'authentification multiples

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US (2) US8481146B2 (fr)
EP (2) EP2137271A1 (fr)
JP (2) JP2010520945A (fr)
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JP2010520945A (ja) 2010-06-17
US20100104826A1 (en) 2010-04-29
WO2008110342A1 (fr) 2008-09-18
US20100038598A1 (en) 2010-02-18
WO2008110317A1 (fr) 2008-09-18
JP2010520828A (ja) 2010-06-17
EP2137272A1 (fr) 2009-12-30

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